JPS5834858A - Aqueous dispersion composition of stilbene direct dye - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which does not gel, has a dyeing effect similar to that of a water-soluble type dye, and is useful for dyeing natural and synthetic fibers, by dispersing a specified stilbene direct dye in the form of a tri(lower alkyl)amine salt or guanidine salt in water. CONSTITUTION:Sodium 4,4'-diaminostilbene-2,2-disulfonate is tetrazotized, and then coupled with phenol to obtain a disazo compd. having a hydroxyl group. This compd. is reacted with an alkylating agent under pressure to form a Na salt dye such as the compd. of formulaI. This Na salt dye is dissolved in water. To the resulting soln. is added a tri(lower alkyl)amine salt or (substd.) quanidine salt. The mixture is stirred to obtain a dye salt of formula II wherein R is CH3, C2H5 or C2H4OH; X is tri(lower alkyl)amine residue or (substd.) guanidine residue. The dye salt of formula II is finely divided and dispersed in water in the presence of a surfactant to form the titled compsn. EFFECT:This compsn. can be diluted and dispersed in water in any ratio without heating. Even when it adheres to the human body, it can be easily washed off with water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous dispersion composition containing a water-insoluble salt of a stilbene direct dye as an active ingredient.

Conventionally, the disazo dye represented by the following formula, 110.8 is ta! It is called Sophene dye, and is used for cellulose I1M in real rust, medium hemp, paper pulp, etc.
It is well known as a direct dye that dyes materials made of
KsiPIN? 4? OCal & 011I heat fi6*), even dilute aqueous solution of eesi degree less than 4sc becomes gel-like and loses its properties, causing problems in weighing during the tF period. Is my best friend, in order to stop this, Il! In this way, a heating device for the stock wi*o gelatinized fat soil is required.In this way, 1 is not only economical but also energy saving. Therefore, when it comes to wrinkle dyes, it is desired that the concentrated solution-like product should be molded into a molded dispersion-like product.

However, for concentrated solution products, the dye OS
* Solubility and dilute aqueous clear liquid aJI gelling property t) II-Minisol O preparation is extremely difficult to prepare, and for aqueous dispersion products I-C are: dye O sulfoyl group and calcium Salts of alkaline earth metals, such as chlorine, chloride, etc., or heavy metals, such as modapden, tungsten, etc., i.e., pigments called 40, are used in such a state. However, to date, there is no known aqueous dispersion product containing the active ingredient of the O dye salt of the present invention.
Without taking the above into consideration, we found that the results of Eidou's research showed that the dye O can form a salt with the sulfonic acid group as defined in the above-mentioned formula. In other words, the present invention is based on the following general formula ( In the formula, l is a methyl group, an ethyl group or a hydroxyethyl group, A guanidine residue which may be substituted with a - group, or a large daanidine member group which may be substituted with a phenyl group or a methyl group. ) The present invention relates to an aqueous dispersion composition characterized by containing as an active ingredient a salt of a stilpene dye represented by the above formula, and the lower alkyl group mentioned above is preferably one of 01 to 04.

Compared to conventional water-soluble powder products, the results of this dyeing process are no different from those of conventional water-soluble powder products.
When in use, 1) It is easy to measure, and it is possible to measure not only weight but also volume.

2) Dyeing 1 because it can be easily diluted and dispersed in cold water at any ratio.
101111 is easy OS) Stockrii does not gel and loses fluidity 〇ri Dyeing bath 1Ill#! When dyeing or stock*, dyeing energy can be saved as there is no need for otIAl & equipment.
6) Even if the dispersion adheres to the body, it falls off more easily when washed with water than conventional crystals. In addition to the above-mentioned advantages in use, the dispersion-like product also has 1, e.g., drying,
This is a grinding process, which saves energy.

Benefits such as no dust contamination of the surrounding area and the ability to maintain a good working environment are also extremely significant in terms of energy saving and occupational health.

The tit dye salt of the present invention represented by the above general formula can be produced in the following manner. 1 molecule ratio, 4. ．． The hydroxyl group of a disazo compound having a hydroxyl group obtained by subjecting sodium 4'-diaonostilbene-2,2'-disulfonate to tetrazotization by a conventional method and coupling 2 molecules of phenol to this in an alkaline manner, for example, 2 The dye thus obtained is reacted under pressure with an alkylating agent such as ethyl chloride in molecular proportions (0%).
17 cum salt filter cake (approximately 150 t of dye sulfur in terms of powder) 9 Contains um salt) 1 approximately 20 times t (vs. dye sulfur) 9
After boiling with water (powder weight of salt) and completely dissolving it, the amount required to form a salt with the sulfone salt of scissor dye.
* indicates an excessive amount of amine salt or unsubstituted 't*
, add substituted aedin salt. Almost immediately S*
The dye salt formed is precipitated, but after stirring and cooling to room temperature to around 50°C, the formed dye salt is separated and r
Wash thoroughly with water until t becomes neutral.

The dye salt thus obtained can be mixed with water and a suitable surfactant in the usual manner, for example by adding glass peas; stirring vigorously for a long period of time will result in a finer dispersion. When it is possible to use a dispersion stabilizer vh
is a known auxiliary agent or additive for O-dispersion compositions, such as preservatives, which are usually used in O-dispersion. Examples of activators include nonionic or anionic activators, but common nonionic activators are used. Preferred dispersion stabilizers include ribinylpyrrolidone, Known film-preserving colloid agents such as OMO can be mentioned.

Examples of the tri-lower alkyl acene, unsubstituted or substituted guanidine used to prepare the dye salt represented by the above general formula are as follows.

1'(01ls)s 11(0111
g) @11(n-03Hy)sll(n-OaH*)
Among the above-mentioned tri-lower alkylamines, unsubstituted or substituted guanidines, tri-lower alkylamines, especially tri-lower alkylamines, especially tri-lower guanidines, are preferred in the preparation of the aqueous dispersion composition of the present invention. In the salt-forming reaction, the above-mentioned tri-lower alkylamines or substituted or unsubstituted guanidines are usually used in the form of hydrochloride, sulfate, μ-scale salt, or the like.

The dye salt represented by the above general formula is wood lIA or hemp,
In addition to cellulose fiber materials such as paper and valves, natural protein fiber materials such as wool and Fx silk, materials made of synthetic polyacetate such as Nisin, and materials made of polyvinyl alcohol, etc. It is also useful for dyeing or coloring so-called amino resins such as raw resin, melamine resin, pendiguana resin, or resins made of mixtures of these resins.

Below are examples of the production of the dye salt represented by the above general formula, examples of the preparation of the aqueous dispersion composition O of the present invention containing the scissors dye salt as an active ingredient, and an aqueous iron dispersion composition IDfII!
〇Production example of dye salt (salt formation reaction 2) Dye salt production example (salt formation reaction 2) A C percake of the dye (about 1507
The water content of about 60% (0%) containing the dye is boiled and dissolved while stirring with water in an amount about 20 times the weight of the dye powder,
Triethylamine y6 in this? t (txs
iuh amount oHt s times) sulfate with 7 equivalents of sulfuric acid is added. Almost immediately, a candy-like dye salt precipitates out, but when left to cool while stirring, it gradually solidifies into crystals.At around 050°C, this crystal kP is separated, and F
Wash thoroughly with water until lllll becomes neutral. In this way, a filter cake of dye salt having a water content of about 40 mm and having the following formula is obtained.

The entire dye salt C) filter cake obtained in the above production example was mixed with 200 tons of water, 2f of a nonionic surfactant consisting of a condensation product of ethylene oquinide and nonylphenol, and a dispersion stabilizer LSt. Particle size approximately a5~t2
In a flask containing about 400 wItt of Shino Glass Peas, stir vigorously with a household appliance to atomize and disperse. The average particle size of the bale dye salt when opened at about 72 hours is less than 5μ! , 1 Stable aqueous dispersion composition is obtained After separating and removing the glass beads tF, water is added to adjust the total composition to 14009. The aqueous dispersion composition thus obtained is the same as the aforementioned seed material [
It can be dyed yellow or greenish yellow.

Similarly, dye salts tm in which R and I in the above general formula are represented by the components listed in the following table were prepared, and aqueous dispersion sets g-1m were respectively prepared.

1. Cotton fabric - Dyeing onto HIM The aqueous dispersion composition of the present invention described in Section 5 was used to dye a multi-cotton fabric according to the following recipe.

Aqueous dispersion composition No. of the present invention S 04% (based on fiber weight) Bath ratio 1:40 (#) Auxiliary agent (mirabilite) 2a011 (#) Dyeing temperature, time 90-95°C, 10 minutes in this manner A nine cotton broadcloth dyed in yellow with medium-glimmer was obtained.

2) Coloring of paper or pulp (internal addition method) The weight ratio of softwood pulp and hardwood pulp is 1=S,
Using pulp with a pulp brightness of 91 (@! If the whitening of the Gnesium O standard white board is t100), the pulp density is 5! 1 (by weight), and the following ingredients are added to the aqueous dispersion composition of the present invention MO, 3α5 (relative to pulp weight) sizing agent (pine resin LO#() aluminum sulfur) After adding LO(), the pulp composition was adjusted by adding water so that the paper pulp concentration was aSS (weight).
The paper thus obtained was colored yellow at the edges.

5) Coloring of paper (size press method) Starch - Podavinyl alcohol 21 Aqueous dispersion composition of the present invention MO, 6 (L5y Water 1t5
The above formulation for a nizing press was uniformly coated on high-quality paper at room temperature using a Mo wire rod of 4 f so that the coating weight was 1.5 f/-. Next, this is the t-drum.
Dry it in the dryer. In this way, high-quality paper colored brightly yellow was obtained. ◎ Diurea resin O Colored urea 22@t Formalin (57%, neutral) 420y Medium Namethylenetetrabenzene 10I The above formulation O
Pulp 47F zinc stearate (L14#) was added to the resin liquid obtained by heat-reacting the mixture, and further, the present invention was added so that the CL5 was high relative to the weight of the final molding resin composition. Aqueous dispersion composition No.
131 and knead well in a kneader. The kernel mixture was dried in a hot air dryer at 80° C. for 5 hours, and then ground in a T-pot mill to obtain a synthetic Pfi urea fat composition.

When this was shaped by a known method, a uniform bright yellow colored urea tree*&shaped object was obtained. ◇ 5) Dyeing of polyamide fiber material Aqueous dispersion composition of the present invention Fiber weight) 4
0 Chronic Vinegar #210p (z bath ratio 1.5G) Put the nylon plain fiber cloth into the dyeing bath with the above recipe,
Stain for ~95C''e5Ω.

Next, thoroughly wash with water and dry to obtain a nylon plain weave dyed in orange yellow. Government Haruki Shimada 1, LJ 271 No. 1981 Patent Application No. 132583 2, Invention 7 Title: Aqueous dispersion composition of stilbeno-based direct dye 3, Person making the supplement = Relationship with Item Ii Patent Representative of applicant Kirie Matsumoto 4 Agent 111 1 Toranomon, Minato-ku, Tokyo 1'1J24 11-5 Lottery 11 - Dutch ordinance date Voluntary amendment 6, number of inventions increased by amendment None /”-1f
＼ <1) Contents of amendment in column a of “Detailed Description of the Invention” of the specification (1) Changed the statement “It is a pulverization step,” in the third line of page 6 of the specification to ``Indication that the pulverization step is omitted. I can do it, so I correct it to -1.

Claims (1)

[Claims] The following general formula (in the formula, or a methyl group, an ethyl group, or a hydroxyethyl group, 1. An aqueous dispersion composition containing as an active ingredient a salt of a stilbene direct dye represented by guanidi/residue.